JPH02225437A - Optical resolution of phenylindanedicarboxylic acid and aromatic polyamide using optical activator thereof - Google Patents

Abstract

PURPOSE:To carry out optical resolution by using optically active D-(-)-pantoyl lactone to give a novel diester derivative of (+ or -)-1,1,3-trimethyl-3- phenylindanedicarboxylic acid and recrystallizing the derivative by taking advantage of difference in solubility. CONSTITUTION:(+ or -)-1,1,3-Trimethyl-3-phenylindanedicarboxylic acid is reacted with optically active D-(-)-pantoyl lactone to give a novel diester and a novel dicarboxylic acid of (+ or -)-1,1,3-trimethyl-3-phenylindanedicarboxylic acid is obtained by taking advantage of difference in solubility. An aromatic polyamide (having at least 0.5g/dl intrinsic viscosity obtained by measuring a solution of 0.5g aromatic polyamide in 100ml dimethylacetamide at 30 deg.C) comprising a polymer having a repeating unit shown by formula I (Ar is group shown by formula II or formula III; n is number of repeating units; * is asymmetric carbon) can be produced by using this novel monomer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a method for producing (+)-1,1,3-trimethyl-3-phenylindane dicarboxylic acid by optical resolution and a method for producing the optically active dicarboxylic acid. This invention relates to a novel aromatic polyamide used.

[Conventional technology]

Aromatic polyamides (hereinafter abbreviated as aramids) have recently attracted attention as heat-resistant polymers.

Generally, aramid is difficult to spin or form into a film due to its insolubility in organic solvents and high softening temperature.

One possible method to improve the solubility of aramid is to introduce a sterically bulky group into the main chain of the polymer, and based on this idea, Reno developed 1.1.3-trimethyl-
For example, polyimide (Ciba-Getgy'5), which is soluble in organic solvents and has a high glass transition temperature, has been synthesized.
XU-2L8), polyester (joint venture, J, Poly,
Sct, Poly, Chem, Hd.

198B, 22.1319) and aramid (J, Cy
WiJson+J.

Po1y, Sci,, Po1. y, Chem, Ed, 1
975.13.749) is publicly known. Although there is an asymmetric carbon in the phenylindane skeleton, no attempt has been made to synthesize optically active polymers with this in mind.

[Problems to be Solved by the Invention] An object of the present invention is to provide a method for producing optically active (+)-1,,1゜3-trimethyl-3-phenylindanedicarboxylic acid by optical resolution, and a method for producing the optically active dicarboxylic acid. An object of the present invention is to provide a novel optically active aramid using.

[Means to solve the problem]

As a result of extensive research to achieve the above object, the present inventors have discovered that optically active (+)'-1. i.

3-trimethyl-3-phenylindanedicarboxylic acid (
Discovered a manufacturing method for (hereinafter abbreviated as (+)-PID),
Furthermore, the present invention was completed by successfully synthesizing a new optically active aramid that is a mm-thick version of the optically active form.

That is, the present invention provides (±)-1,1,3-)dimethyl-3
-Optically active with phenylindane dicarboxylic acid-(-
)-1,1 by recrystallization using the difference in solubility of diester derivatives obtained from pantoyllactone.
, 3-) Dimethyl-3-phenylindane dicarboxylic acid is separated (±)-1,1,3-) Dimethyl-3-phenylindane dicarboxylic acid optical resolution method and (±)- produced by the optical resolution method 1) -(-) of 1,1,3-)dimethyl-3-phenylindanedicarboxylic acid
-pantoyllactone diester derivative or (+)
-1,1,3-trimethyl-3 phenylindane dicarboxylic acid or a polymer having a repeating unit represented by the following formula, and has an opening viscosity (dimethylacetamide 100
FJ! 3 with a solution of 0.5 g of aromatic polyamide dissolved in
measured at 0 °C) (η1,) is at least 0.5 g/
d l optically active aromatic polyamide is provided.

2, n is the number of repeating units, and * represents an asymmetric carbon.) The optical resolution of the present invention will be explained according to the following procedure.

The raw material (±)-PID is commercially available from Amoeo and other companies and is therefore easily available. First of all, the raw materials (±)
- converting the PID into the corresponding acid chloride in the usual manner; The corresponding diester derivative can be obtained by dropping a solution of this acid chloride into a solution of optically active -(-)-pantoyl lactone while stirring slowly in the presence of an amine. By recrystallizing this diester derivative using an appropriate solvent and taking advantage of the difference in solubility, (+)-
Only the diester derivative of PID can be preferentially separated, and pure (+)-PID can be easily obtained by hydrolyzing this (+)-diester derivative.

As a method for converting (+)-PID to acid chloride,
(±)-PID can be converted to the corresponding acid chloride by reaction with excess thionyl chloride in the presence of a catalytic amount of dimethylformamide. The amount of thionyl chloride used in this case is at least 2 equivalents relative to (±)-PID. Even if a large excess of 10 equivalents or more is used, the yield remains unchanged and is not economical.

The amount of D-(-)-pantoyl lactone used is at least 2 equivalents or more relative to (±)-PID. Even if a large excess of 8 equivalents or more is used, the yield remains unchanged and is not economical.

Examples of amines added to trap hydrochloric acid generated during the reaction include amines such as triethylamine, pyridine, and lutidine. The amount of amine used is (
±)-2 equivalents or more relative to PAD. Even if a large excess of 8 equivalents or more is used, the yield remains unchanged and is not economical.

The solvent may be any solvent as long as it dissolves pantoyllactone and PID, but preferably halogenated solvents such as chloroform, carbon tetrachloride, methylene chloride, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. It is an aprotic polar solvent such as

The reaction is carried out at a temperature range of 0 to 35°C, preferably 15 to 25°C, with stirring for 1 to 10 hours, preferably 4 to 8 hours.

After the reaction is complete, the product can be isolated by conventional esterification post-treatments. For example, after the reaction is completed, the reaction solvent is washed sequentially with a dilute aqueous hydrochloric acid solution and water, and after drying with an appropriate desiccant, the solvent is distilled off, and (±)-P
A crude product of diester derivative of ID is obtained. Colored by-products are removed from this crude product using silica gel using methylene chloride as a developing solvent to obtain a white solid.

By washing this white solid with ethanol (Sat)
-Remove the monoester derivative of PID and target (
A diester derivative of ±)-PID is obtained.

By repeating recrystallization from hot ethanol several times, this diester derivative is made optically pure (+)-
The diester derivative of PID is obtained as colorless crystals with a melting point of 225-226°C. The isolated product is confirmed to be a diester derivative of D-(-)-pantoyl lactone of (+)-PID by optical rotation, 'tl-NMR, IR, etc.

This diester derivative is easily converted into dicarboxylic acid by hydrolysis under normal alkaline conditions. Optical rotation, ')l-NMI? , pure (+) by rR
-W1 recognizes that it is a PID. Examples of the alkaline aqueous solution include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, and calcium hydroxide. The concentration of the aqueous solution is 1 to 20
%, preferably in the concentration range of 1 to 10% by weight.

By directly reacting the optically active (+)-PID obtained by the above method with various diamines in the presence of triphenyl phosphite, pyridine, and sodium chloride, various new optically active aramids are produced. Can be synthesized.

Examples of diamines include m-phenylenediamine, p-phenylenediamine, bis(4-amino)methane, bis(4-amino)methane, and bis(4-amino)methane.
Examples include aromatic diamines such as -amino)ether. The amount of diamine used is 1.0 equivalent relative to the dicarboxylic acid.

The synthesis reaction includes 2.0 equivalents or more of triphenyl phosphite, 2.0 equivalents or more of lithium phosphite, 6.0 equivalents or more of pyridine,
Further, by adding an appropriate amount of N-methylpyrrolidone as a solvent, under a nitrogen atmosphere, 80 to 160'C1, preferably 90 to
It is completed by continuing stirring at a temperature range of 120°C for 1 to 8 hours. The produced aramid can be purified by a conventional reprecipitation method. This aramid is confirmed to be the desired optically active aramid because its IR and IIMR agree with that of an aramid synthesized from a racemate, and it also exhibits optical rotation.

Moreover, the intrinsic viscosity of the optically active aramid of the present invention (η!7.
) is at least 0.50 g/d1 or more, preferably 0
．． 60g/d1. That's all. Intrinsic viscosity is 0.5
If it is less than 0g/11, the degree of polymerization is low and it is difficult to form into films or molded articles, which limits the range of applications of this optically active aramid. The intrinsic viscosity was measured at 30° using a solution of 0.5 g of the optically active aramid of the present invention dissolved in dimethylformamide or 4 sulfur u l
It was determined by measuring at C.

〔Example〕

The present invention will be specifically explained below using Examples.

(±)-1,,1,3-)Samethyl-3 was added to a solution of 28.6 g of 1 g of diester f-(-)-pantoyl lactone and 22.2 g of triethylamine dissolved in about 500 ml of methylene chloride. Riphenylindane dicarboxylic acid chloride 36゜1
A solution of 200 g of methylene chloride was slowly added dropwise. After stirring at room temperature for 5 hours, the reaction mixture was washed successively with 2001 d of diluted hydrochloric acid solution and 200 ml of water, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the dull brown crude product was dissolved in methylene chloride as a developing solvent at 200 °C.
Purified on silica gel. The purified white solid was washed with ethanol and dried to yield 38.0 g of (±)-P I
A diester derivative of D was obtained.

1 (-N month R (CDCl 3) δ1.04 (s, 3)
1), 1.21.1.22X(s, 311),
126. 1.28X(s, 31ri, i, 2
9. 1.30(s+314), 1.38(s,
3! i), ], 73X, 1.74(s
, 3H), 2.24-2.60 (m, 21
1), 4.11 (d,, 2H, J=2.7Hz),
5.6Hd.

Ifl, J=5.4Hz), 7.24~8.08(
+n, 7H) (where 8 is (peak due to diester derivative of +1-PID) IR2970,1795 (lactone C-0) 17'29 (ester C=0) cta-'
20 g of the ester derivative was taken in a vacuum, completely dissolved in 3.200 d of hot ethanol, and then cooled slowly. After standing for - days, the precipitated crystals were separated by filtration and dried to obtain 8.5 g of crude crystals of a diester derivative of (+)-PID.

The optical rotation ([α]D) of this crude crystal was measured in tetrahydrofuran (TIIF).

[α]. +110~130 (co, 5, THP
) 8.5 g of this crude crystal was heated again with 650111 ethanol.
completely dissolved and slowly cooled. After half a day, the precipitated crystals are separated by filtration and dried to form optically pure (+)
4.5 g of a diester derivative of -PID was obtained.

The optical rotation of this purified crystal was measured in the same <THF.

[α3 o+204 (co, 5, THF)'f
l-NMR(CDCl3)δ1,04(s,3)1
), 1.21 (s, 311).

1.23 (s, 3H), 1.27 (s, 3H),
1.28(s, 38), 1.37(!!, 31
1), 1.74 (s, 3H), 2.28 (d,
IH, J = 15Hz).

2.49 (d, ], H, J=15Hz), 4.1.
Hd. 2B, J.2.7iiz).

5.61 (d, IH, J=5.4Hz), 7. ．． 2
4-8.08 (ai+ 78) IR2970, 1750
(lactone C-0) 1731 (ester C'=0)
cm-'2 ■'' (±)-Disperse 5.0 g of the diester derivative of PID in 30 d of ethanol, and add 10 g of a 3% aqueous sodium hydroxide solution.
Added 0d. This solution was heated under reflux for 3 hours, and then cooled to room temperature. To the resulting transparent solution, an aqueous IN hydrochloric acid solution was added until the solution became acidic to precipitate (+)-PID. 2.81 g of (+)-PID crystals precipitated by filtration (
95%).

・ 13 Aramid (+)-PIDI, 62g 1 bis(4-aminophenyl)ether 1.00g, lithium chloride 0.5g, triphenyl phosphite 2.65aj! , pyridine 2.5 ra
A mixture of l,N-methylpyrrolidone 10- was heated to 100"C under nitrogen atmosphere and stirred for 3 hours. After cooling, the reaction mixture was added dropwise to 5001d! of methanol, and the precipitated product was separated by filtration and heated. By washing with methanol and drying under reduced pressure, 2.44 g of optically active aramid (
99%). Viscosity, glass transition temperature (Tg), decomposition temperature (Td), [α] of the optically active aramid produced. are summarized in Table 1.

The corresponding optically active aramid was obtained by direct polymerization of 1-Sijiedu (+)-PID and p-phenylenediamine according to the method shown in Example 3. Viscosity, Tg, T of the optically active aramid produced
d, (α], are summarized in Table 1.

Example 11 Shadow (±)-PfD and m-phenylenediamine were directly polymerized by the method shown in Example 3 to obtain the corresponding optically active aramid. Viscosity, Tg, T of the optically active aramid produced
d, (α]. are summarized in Table 1.

EXAMPLE - (+)-PrD and bis(4-aminophenyl)methane were directly polymerized by the method shown in Example 3 to obtain the corresponding optically active aramid. The viscosity, Tg, Td, and (α) of the produced optically active aramid are summarized in Table 1.

〔Effect of the invention〕

The optically active group (+)-phenylindane dicarboxylic acid of the present invention has a wide range of uses as a new monomer, and the optically active aramid of the present invention is not only a solvent-soluble heat-resistant polymer but also optically active. Needless to say, it can be used for electronic materials and dividing agents.

Claims (1)

[Claims] Utilizes the difference in solubility between diester derivatives obtained from 1,(±)-1,1,3-trimethyl-3-phenylindane dicarboxylic acid and optically active D-(-)-pantoyl lactone. (+)-1,1,3-trimethyl-3-phenylindane dicarboxylic acid is separated by recrystallization. Optical resolution method. 2. (±)- produced by the optical resolution method according to claim 1
D-(-)-pantoyllactone diester derivative of 1,1,3-trimethyl-3-phenylindanedicarboxylic acid. 3. (±)- produced by the optical resolution method according to claim 1
1,1,3-trimethyl-3-phenylindane dicarboxylic acid. 4. Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Ar in the formula represents the formula▲There are mathematical formulas, chemical formulas, tables, etc.▼, n is the number of repeating units, and * represents an asymmetric carbon. ) consisting of a polymer having repeating units represented by
Optically active aromatic polyamide having an intrinsic viscosity of at least 0.5 g/dl.